EP0437405A1 - Verfahren und Gerät zur Bestimmung des Gesamtstickstoffes - Google Patents

Verfahren und Gerät zur Bestimmung des Gesamtstickstoffes Download PDF

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Publication number
EP0437405A1
EP0437405A1 EP91400053A EP91400053A EP0437405A1 EP 0437405 A1 EP0437405 A1 EP 0437405A1 EP 91400053 A EP91400053 A EP 91400053A EP 91400053 A EP91400053 A EP 91400053A EP 0437405 A1 EP0437405 A1 EP 0437405A1
Authority
EP
European Patent Office
Prior art keywords
sample
nitrogen
catalytic mass
catalytic
oven
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP91400053A
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English (en)
French (fr)
Inventor
Guy Bonometti
Roland Olivier
Jacques Maurice
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Societe National Elf Aquitaine
Original Assignee
Societe National Elf Aquitaine
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Societe National Elf Aquitaine filed Critical Societe National Elf Aquitaine
Publication of EP0437405A1 publication Critical patent/EP0437405A1/de
Withdrawn legal-status Critical Current

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/12—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using combustion
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/17—Nitrogen containing
    • Y10T436/176152—Total nitrogen determined
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/17—Nitrogen containing
    • Y10T436/176152—Total nitrogen determined
    • Y10T436/176921—As part of an elemental analysis

Definitions

  • the invention relates to the rapid determination of total nitrogen in various media, in particular in waste water and others. It includes a new method for carrying out such analyzes, as well as an apparatus for carrying it out. These methods and apparatus are particularly useful for the permanent control of pollution of urban or industrial waters; it easily makes it possible to appreciate total nitrogen contents as low as, for example, 100 ppb, with great rapidity, whatever the chemical form in which this nitrogen is found.
  • the present invention provides an important improvement in this field, by making it possible to very quickly monitor the total nitrogen content of a given medium; the results are easy to record and can represent dozens of analyzes per day.
  • the process according to the invention which comprises the combustion of the nitrogenous materials of a sample, is characterized in that a sample of the compounds to be dosed, volatilized, is passed in contact with one or more catalytic masses, metallic, carried at high temperature, in the presence of oxygen, so as to convert the nitrogen compounds in the sample to NO, and then determine the amount of NO formed, by a process known per se.
  • the metal is stainless, such as Fe-Ni, Fe-Ni-Cr steel, optionally containing V, Mo , W, Co, Nb, Ti etc.
  • the heating resistor can be made of W or an alloy of this metal, in particular with one or more of the above-mentioned metals.
  • the metals of the platinum group, Pt-Ir, etc. are well suited. and very particularly rhodium platinum, for example 90% Pt-10% Rh, preferably in wires serving as a heating resistance.
  • the process is carried out in such a way that contact with the gaseous phase passed over the heated catalyst is as intimate as possible; for this it is preferable that the thickness of the gaseous layer, traveling in contact with the metal, not exceed 3 mm, and - the better - that it is between 0.3 mm and 2 mm, and particularly between 0, 5 and 1.5 mm.
  • the contact time between the catalyst and the gas flow, carrying the materials to be analyzed, at temperatures of the order of 800 ° to 1200 ° C, is generally from 0.2 to about 3 seconds; at preferred temperatures of 900 ° to 1000 ° C., it is desirable that this contact time be of the order of 0.5 sec to 2 sec and especially from 0.5 to 1 sec.
  • the metal surface, in particular PtRh should be from 5 to 40 cm2, and preferably from 7 to 9 cm2.
  • the nitrogen compounds, whatever they are, are converted only to NO, thanks to the catalytic effect of the metal on which they are passed at high temperature.
  • the heating can be carried out by an appropriate means, other than the passage of the current in the catalyzing metal; or else, this external heating is auxiliary to that produced by the catalyst metal itself.
  • the sample to be analyzed being introduced into the catalyzing space, hot, in the form of a solution
  • the latter can be aqueous or organic; in other words the nitrogenous compound (s) are in solution or dispersion in water or in an organic solvent, for example alcohol, ketone, ester, hydrocarbon or other, to the exclusion - of course - of amines, amides and other compounds nitrogen.
  • an organic solvent for example alcohol, ketone, ester, hydrocarbon or other
  • the invention also applies to solid or pasty samples, provided that they can be volatilized while hot , in a stream of oxygenated gas.
  • the solid sample is placed in a basket at the entrance of a suitable oven and subjected to the gas current, as are the liquid samples.
  • an electrolyte to the sample of material to be analyzed. More particularly, the precision is increased by the introduction of a halide, in particular a fluoride, chloride or bromide of alkali or alkaline-earth metal.
  • a halide in particular a fluoride, chloride or bromide of alkali or alkaline-earth metal.
  • the quantity of electrolyte to be used is not critical, it is good to add about 0.01 to 0.2 equivalent per liter of solution to be analyzed, the preferred proportion being generally of the order of 0, 05 to 0.15 eq.
  • salts such as NaCl, KCl, CaCl2 or / and MgCl2 are particularly suitable.
  • halogenated hydracids also act in the direction of improving the accuracy of the measurements, but - as their use leads to the acidification of the gas stream and the release of halogen, harmful to the apparatus - it becomes necessary to carry out a subsequent neutralization. It is therefore much more practical to use the neutral salts mentioned above.
  • the latter is assayed by any method known per se.
  • the chemiluminescence produced by the reactions is very well suited for this purpose: used in the device of the companies SERES and ENVIRONNEMENT SA Another good method is based on optical interferometry. (SERES device, ELF-ANVAR license) These methods being known in the art, there is no need to describe them here.
  • the apparatus according to the invention which comprises an oven with heating means at or above 800 ° C, and means for blowing an oxygenated gas in this oven, is characterized in that the oven contains a catalyst charge for the oxidation of nitrogen compounds selectively to NO oxide; the apparatus includes a device for dosing NO in the gas which has passed through the furnace.
  • the enclosure of the oven is made of refractory material, such as porcelain, alumina, quartz or the like, or else of metal, for example stainless steel. It is heated externally, using an electric or gas winding, internally by a resistance or heating rod, or - possibly - both from the outside and the inside.
  • a suitable catalyst in the path of the gas passed through the oven, this catalyst is placed in the enclosure of the oven, so as to be in the most intimate contact possible with the gas.
  • a catalytic mass can fill all or part of the enclosure; it can be in the form of balls, rings, turnings, filaments or other parts made with the various catalyzing metals, indicated above.
  • wires or fibers of catalyst metal can surround an axial heating rod.
  • a very interesting embodiment which has given remarkable results, consists in using catalyst metal wires both as a catalyst and as an electric heating resistance. It has been particularly successful with rhodium platinum at 10% Rh.
  • volatilization chamber provided at the inlet of the oven; this chamber is intended to receive the sample to be analyzed and to bring it to the high temperature at which it becomes entrainable by the current of oxygenated gas towards the interior of the oven.
  • the volatilization chamber has a heating system independent of that of the rest of the oven, and - consequently - adjustable separately.
  • an embodiment according to the invention provides a tube in line with the volatilization chamber, making it possible to introduce an injection tube or needle, to bring the sample substantially to the middle of the heating resistance of the chamber; preferably a network of refractory fibers, in particular asbestos, is then placed inside heating coils, to distribute the sample well in the volatilization chamber.
  • FIG. 1 we see the quartz tube furnace, consisting of a tube 1 terminated at its ends by enlarged parts or "tulips" 2 and 2 ′.
  • the tulip 2 are arranged turns 3 in Pt at 10% Rh and between them are placed asbestos fibers.
  • the tulip 2 carries a lateral tube 5 through which the liquid sample is introduced by means of a microsyringe; this is chosen to be long enough, so that its tip penetrates the middle of the set of turns 3 where the asbestos distributes the injected liquid well and cleans the tip of the needle.
  • a tube 6 passes, bringing the oxygen which is blown towards the interior of the oven, throughout the analysis.
  • a second heating resistor 4 similar to 3 wound on a porcelain rod occupies the entire length of part 1 of the oven and ends inside the tulip 2 ′.
  • the drawing shows the terminations of the two heating resistors, which lead to sockets and to regulating devices in the known manner.
  • Figure 2 shows how the oxygen entering the furnace at 6 is admitted through a valve 8, then passes through a drying column 9 and through a flow meter 10, before arriving at 6.
  • the gases pass through a layer of adsorbent silica ("Silicagel") of the interchangeable tube 11, then the desiccant columns 12-12 ′ and a flow meter 13 from which, by a pipe 14, they are passed through a nitrogen oxide analyzer 15 (Fig. 3).
  • Silicagel adsorbent silica
  • the entire analytical installation is represented by the diagram in Figure 3.
  • the NO detector, reference 15, used was mainly a chemiluminescence or optical refractometry device.
  • a conventional recorder 16 completed the assembly.
  • the temperature inside the oven was from 900 ° to 1000 ° C.
  • 5 to 20 ⁇ l of sample solution were injected.
  • the oxygen flow rate was set at about 13 l / h.
  • the response time was 25 sec.
  • the measurement range was between 0.1 and 20 mg / l.
  • the table below gives the results of analysis of various nitrogen compounds: an accuracy of about ⁇ 8% is found on average. In another series of similar measurements, but after the addition of 5 g NaCl to the solutions of the samples, the precision comes out to ⁇ 1.6%.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
EP91400053A 1990-01-12 1991-01-11 Verfahren und Gerät zur Bestimmung des Gesamtstickstoffes Withdrawn EP0437405A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9000312 1990-01-12
FR9000312A FR2657166B1 (fr) 1990-01-12 1990-01-12 Procede et appareil pour la determination de l'azote total.

Publications (1)

Publication Number Publication Date
EP0437405A1 true EP0437405A1 (de) 1991-07-17

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EP91400053A Withdrawn EP0437405A1 (de) 1990-01-12 1991-01-11 Verfahren und Gerät zur Bestimmung des Gesamtstickstoffes

Country Status (4)

Country Link
US (1) US5185268A (de)
EP (1) EP0437405A1 (de)
CA (1) CA2034066A1 (de)
FR (1) FR2657166B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1007860C2 (nl) * 1997-12-19 1999-06-22 Euroglas Bv Werkwijze en inrichting voor het analyseren van een monster.

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6096267A (en) * 1997-02-28 2000-08-01 Extraction Systems, Inc. System for detecting base contaminants in air
DE69816277T2 (de) * 1997-02-28 2004-06-03 Extraction Systems, Inc., Franklin System zum nachweis von aminen und anderen basischen molekularen verumreinigungen in einem gas
US6251679B1 (en) * 1998-10-26 2001-06-26 Aerodyne Research, Inc. Method for measuring pollutant formation
US6207460B1 (en) 1999-01-14 2001-03-27 Extraction Systems, Inc. Detection of base contaminants in gas samples
US6503956B2 (en) * 2001-01-11 2003-01-07 Chevron U.S.A. Inc. Determination of heteroatom content in Fischer-Tropsch wax
US7392857B1 (en) * 2007-01-03 2008-07-01 Hall David R Apparatus and method for vibrating a drill bit

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2434930A1 (de) * 1973-07-19 1975-02-13 Beckman Instruments Inc Verfahren und anordnung zum nachweis und zur messung des stickstoffgehalts einer probe
DE2621616A1 (de) * 1975-05-15 1976-12-02 Sumitomo Chemical Co Analytisches verfahren und vorrichtung zur bestimmung des gesamt-stickstoff- und/oder -kohlenstoffgehalts in waessrigen systemen
FR2415299A1 (fr) * 1978-01-19 1979-08-17 Sumitomo Chemical Co Procede analytique et dispositif pour la determination des teneurs totales en azote dans des systemes aqueux
EP0020072A1 (de) * 1979-05-23 1980-12-10 Sumitomo Chemical Company, Limited Analytisches Verfahren und Vorrichtung zur Bestimmung des Gesamtstickstoffgehaltes einer Probe
US4333735A (en) * 1981-03-16 1982-06-08 Exxon Research & Engineering Co. Process and apparatus for measuring gaseous fixed nitrogen species
EP0075467A1 (de) * 1981-09-18 1983-03-30 Sumitomo Chemical Company, Limited Verfahren zum Analysieren von Stickstoffspuren

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3877875A (en) * 1973-07-19 1975-04-15 Beckman Instruments Inc Nitrogen constituent analysis
US4018562A (en) * 1975-10-24 1977-04-19 Antek Instruments, Inc. Chemiluminescent nitrogen detection apparatus and method
US4066409A (en) * 1977-01-19 1978-01-03 Thermo Electron Corporation Method and apparatus for chromatographically analyzing a liquid sample

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2434930A1 (de) * 1973-07-19 1975-02-13 Beckman Instruments Inc Verfahren und anordnung zum nachweis und zur messung des stickstoffgehalts einer probe
DE2621616A1 (de) * 1975-05-15 1976-12-02 Sumitomo Chemical Co Analytisches verfahren und vorrichtung zur bestimmung des gesamt-stickstoff- und/oder -kohlenstoffgehalts in waessrigen systemen
FR2415299A1 (fr) * 1978-01-19 1979-08-17 Sumitomo Chemical Co Procede analytique et dispositif pour la determination des teneurs totales en azote dans des systemes aqueux
EP0020072A1 (de) * 1979-05-23 1980-12-10 Sumitomo Chemical Company, Limited Analytisches Verfahren und Vorrichtung zur Bestimmung des Gesamtstickstoffgehaltes einer Probe
US4333735A (en) * 1981-03-16 1982-06-08 Exxon Research & Engineering Co. Process and apparatus for measuring gaseous fixed nitrogen species
EP0075467A1 (de) * 1981-09-18 1983-03-30 Sumitomo Chemical Company, Limited Verfahren zum Analysieren von Stickstoffspuren

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1007860C2 (nl) * 1997-12-19 1999-06-22 Euroglas Bv Werkwijze en inrichting voor het analyseren van een monster.
EP0924517A1 (de) * 1997-12-19 1999-06-23 Euroglas B.V. Verfahren und Vorrichtung zum Analysieren einer Probe

Also Published As

Publication number Publication date
FR2657166A1 (fr) 1991-07-19
FR2657166B1 (fr) 1993-04-23
CA2034066A1 (en) 1991-07-13
US5185268A (en) 1993-02-09

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